CN112851346B - Ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and preparation method thereof - Google Patents

Ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and preparation method thereof Download PDF

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CN112851346B
CN112851346B CN202110211647.9A CN202110211647A CN112851346B CN 112851346 B CN112851346 B CN 112851346B CN 202110211647 A CN202110211647 A CN 202110211647A CN 112851346 B CN112851346 B CN 112851346B
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张岱南
王刚
刘成
张怀武
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University of Electronic Science and Technology of China
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Abstract

The invention provides a ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and a preparation method thereof, and the chemical general formula is Mg 1‑ x Cu x ZrNb 2 O 8 X is more than 0 and less than or equal to 0.1, and the crystal phase is pure phase MgZrNb 2 O 8 The method comprises the steps of carrying out a first treatment on the surface of the The microwave dielectric ceramic material is made of MgO, cuO, zrO 2 、Nb 2 O 5 According to the chemical formula Mg 1‑x Cu x ZrNb 2 O 8 Wherein 0 is<Proportioning with the stoichiometric ratio of x being less than or equal to 0.1, ball milling and mixing for the first time, presintering for 2-6 hours at the temperature of 1000-1100 ℃, granulating and molding after ball milling and mixing for the second time, and sintering for 2-6 hours at the temperature of 1150-1350 ℃. The invention adopts Cu ion pair MgZrNb 2 O 8 The Mg site in the ceramic is replaced, and the crystal structure is finely adjusted, so that the lattice energy and the bond energy are enhanced. The Cu ion substitution improves the compactness of the ceramic, and increases the grain size, thereby improving the quality factor of the ceramic material.

Description

Ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and preparation method thereof
Technical Field
The invention belongs to the technical field of microwave dielectric ceramic materials, and particularly relates to an ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and a preparation method thereof.
Background
The microwave dielectric ceramic is mainly applied to microwave frequency bands (mainly UHF and SHF frequency bands, 300 MHz-300 GHz), and is a key material of microwave components of resonators, filters, antennas and the like used for mobile communication, satellite communication, military radars and the like. In order to meet the requirements of miniaturization, light weight, multifunction and low cost of equipment, microwave dielectric ceramics have become one of the hot spots in the research field of microwave dielectric materials at home and abroad, and have attracted great interest to researchers in recent years. In order to meet the requirements of the device, the microwave dielectric ceramic material should meet the following conditions: (1) relatively high dielectric constant: the high dielectric constant can reduce the size of the device and improve the integration level; (2) high quality factor q×f: the high quality factor can effectively inhibit signal attenuation, improve signal to noise ratio, ensure excellent frequency selection characteristic and reduce insertion loss of the device under high frequency. (3) The temperature coefficient of the resonant frequency is good, so that the temperature reliability of the device can be ensured. These requirements have limited the practical use of most ceramic materials to a great extent. Therefore, it is necessary to develop new ceramic material systems.
In recent years, a magnesium zirconium niobate (MgZrNb) 2 O 8 ) The ceramic is a novel low-loss microwave dielectric ceramic newly developed in recent years, and has good microwave dielectric property, thereby attracting wide attention. The microwave dielectric properties are as follows: epsilon r =24.82, q×f=72, 842ghz and τ f = -47.65ppm/°c. However, the sintering temperature is high (more than or equal to 1350 ℃) and the Q multiplied by f value still has room for further optimization. The low-melting-point additive can properly reduce MgZrNb 2 O 8 The sintering temperature of the ceramic, but also introduces a second phase, which in turn reduces the quality factor (Effect of H) 3 BO 3 addition on the sintering behavior and microwave dielectric properties of wolframite-type MgZrNb 2 O 8 ceramics). We therefore conceived how to properly reduce MgZrNb while maintaining phase purity 2 O 8 While reducing dielectric losses. Therefore, the invention adopts Cu ions to modify the microstructure and microwave dielectric property of the microwave dielectric ceramic, and develops the microwave dielectric ceramic with ultralow loss and the preparation method thereof. We found that the results indicate that: the Cu ions can effectively improve the density of the ceramic, promote the growth of crystal grains, and enable the size of the crystal grains to be controllable within a certain range, thereby realizing the regulation and control of the microwave dielectric property.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
ultralow-loss zirconium magnesium niobate bodyThe microwave dielectric ceramic material is a microwave dielectric ceramic material, and the chemical general formula of the microwave dielectric ceramic material is Mg 1-x Cu x ZrNb 2 O 8 Wherein x is more than 0 and less than or equal to 0.1, and the crystal phase is pure phase MgZrNb 2 O 8 。
As a preferable mode, when x is more than or equal to 0.04, the crystal grain form is a rod-shaped structure in a polyhedron; when x is more than or equal to 0.08, the crystal grain form is completely converted into a rod-shaped structure from a polyhedron.
Preferably, x=0.04. The comprehensive performance of the microwave dielectric ceramic material obtained at this time is optimal.
Preferably, the microwave dielectric ceramic material is made of MgO, cuO, zrO 2 、Nb 2 O 5 According to the chemical formula Mg 1- x Cu x ZrNb 2 O 8 Wherein x is more than 0 and less than or equal to 0.1, the materials are mixed by the first ball milling, presintering for 2 to 6 hours at the temperature of 1000 to 1100 ℃, granulating and molding after the second ball milling, and sintering for 2 to 6 hours at the temperature of 1150 to 1350 ℃.
Preferably, the dielectric properties of the microwave dielectric ceramic material are as follows: relative dielectric constant ε r 24-26, the quality factor Qxf is 72,000-140,000 GHz, and the resonant frequency temperature coefficient tau f Is-32 to-50 ppm/DEG C.
The invention also provides a preparation method of the ultralow-loss magnesium lithium niobate system microwave dielectric ceramic material, which comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 、Nb 2 O 5 According to the chemical formula Mg 1-x Cu x ZrNb 2 O 8 Wherein x is more than 0 and less than or equal to 0.1;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the raw materials, a solvent and a ball milling medium are placed in a ball mill for wet ball milling, so that first slurry is obtained;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture for crushing to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000-1100 ℃ for 2-6 hours to enable the uniformly mixed powder to perform presintering reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the raw materials, the solvent and the ball milling medium are placed in a ball mill for wet ball milling, so as to obtain second slurry;
step 6: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 5, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body;
step 7: sintering; sintering the green body obtained in the step 6 for 2 to 6 hours at 1150 to 1350 ℃ to prepare pure-phase Mg 1-x Cu x ZrNb 2 O 8 A ceramic material.
In the step 2, deionized water is used as a solvent for wet ball milling, when zirconium balls are used as ball milling media, the mass ratio of raw materials to the zirconium balls to the deionized water is 1:4-6:2-3, the rotating speed is 200-300 rad/min, and the ball milling time is 2-6 hours; in the step 5, deionized water is adopted as a solvent for wet ball milling, when zirconium balls are adopted as ball milling media, the mass ratio of raw materials to the zirconium balls to the deionized water is 1:4-6:2-3, the rotating speed is 200-300 rad/min, and the ball milling time is 3-5 hours.
Preferably, the drying temperature in the step 3 is 80-110 ℃.
Preferably, the granulating agent in the step 6 is a polyvinyl alcohol aqueous solution, and the mass concentration of the polyvinyl alcohol in water is 12-15%; preferably 12%. In the step 6, the crushing operation is specifically that the granulated sample is sieved by a 100-120 mesh sieve to obtain powder particles.
Preferably, the heating operation in the step 7 is to heat up to 400-600 ℃ from normal temperature at a heating rate of 1-5 ℃/min, keep the temperature for 1-3 hours, and heat up to the sintering temperature at a heating rate of 1-3 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts Cu ion pair MgZrNb 2 O 8 The Mg site in the ceramic is replaced, and the CuO has a low melting point and is similar to the radius of Mg ions, so that the CuO can enter a crystal lattice to promote sintering, fine adjustment is carried out on a crystal structure, and the crystal lattice energy and bond energy are enhanced. In addition, cu ions replace to improve the compactness of the ceramic, and the grain size is increased, so that the quality factor of the ceramic material is improved. According to a specific embodiment, i.e. at a lower sintering temperature, still has extremely excellent dielectric properties, in particular epsilon r ＝24～36，Q×f＝72,000～130,000GHz，τ f -32 to-50 ppm/. Degree.C. In addition, the ceramic material of the invention needs no sintering auxiliary agent, only needs one-time presintering, has simple preparation process and is beneficial to reducing production cost.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of samples of different Cu contents (x=0-0.1) provided in an embodiment of the present invention.
Fig. 2 is an SEM image of samples with different Cu contents (x=0-0.1) according to an embodiment of the present invention.
Table 1 shows the sintering temperatures and microwave dielectric properties of samples with different Cu contents (x=0 to 0.1) provided in the embodiments of the present invention.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Comparative example:
the comparative example provides a microwave dielectric ceramic material, the chemical general formula of which is MgZrNb 2 O 8 The X-ray diffraction (XRD) pattern is shown as a in fig. 1, and the SEM pattern is shown as a in fig. 2; as can be seen from the figure, the grain morphology is polyhedral.
The MgZrNb 2 O 8 The preparation method of the ceramic material comprises the following steps:
step 1: batching; mgO, zrO as raw material 2 And Nb (Nb) 2 O 5 Respectively according to a chemical general formula MgZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: the method comprises the steps of taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:5:2 for wet ball milling, wherein the ball milling time is 4 hours, and the rotating speed is 250rad/s, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in an oven at 80-110 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 4 hours at 1100 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: the zirconia balls are used as ball milling media, deionized water is used as solvent, raw materials, the zirconia balls and the deionized water are placed in a planetary ball mill according to the mass ratio of 1:5:1.5 for wet ball milling, the ball milling time is 4 hours, and the rotating speed is 250rad/s, so that second slurry is obtained;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in an oven at 80-110 ℃, adding 12% polyvinyl alcohol (PVA) aqueous solution into the oven after crushing treatment, granulating through a 80-120 mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; sintering the green body obtained in the step 6 for 4 hours at 1350 ℃, wherein the specific heating operation is as follows: firstly, heating to 500 ℃ at a heating rate of 2 ℃/min,maintaining at the temperature for 2 hours for removing excessive PVA, and then continuously heating the sintering temperature at a heating rate of 2 ℃/min to obtain MgZrNb as a pure phase 2 O 8 Is a ceramic material of the ceramic material.
Example 1:
the embodiment provides a microwave dielectric ceramic material, the chemical formula of which is Mg 0.98 Cu 0.02 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 . X-ray diffraction (XRD) pattern as b in fig. 1, SEM pattern as b in fig. 2; as can be seen from the figure, the grain morphology is polyhedral.
The preparation method of the ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.98 Cu 0.02 ZrNb 2 O 8 Proportioning the stoichiometric ratio, wherein the purity of the raw materials is more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: the method comprises the steps of taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:2 for wet ball milling, wherein the ball milling time is 2 hours, and the rotating speed is 200rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in an oven at 80 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 100-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into a high-purity alumina crucible, presintering for 2 hours at the temperature of 1000 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:2 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 200rad/min, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in an oven at 80 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the second slurry after crushing treatment, sieving the second slurry by a 80-mesh sieve for granulation, and then pressing the second slurry under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; sintering the green body obtained in the step 6 for 2 hours at 1350 ℃, wherein the specific heating operation is as follows: firstly, heating to 400 ℃ at a heating rate of 1 ℃/min, maintaining at the temperature for 1 hour, removing excessive PVA, and then continuously heating the sintering temperature at the heating rate of 1 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 2:
the embodiment provides a microwave dielectric ceramic material, the chemical formula of which is Mg 0.96 Cu 0.04 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 . X-ray diffraction (XRD) patterns are shown as c in fig. 1, and SEM patterns are shown as c in fig. 2; as can be seen from the figure, the crystal grain morphology is a polyhedron coexisting with a rod-like shape.
A preparation method of a ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.96 Cu 0.04 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:3 for wet ball milling, wherein the ball milling time is 6 hours, and the rotating speed is 300rad/s, so as to obtain first slurry;
step 3: drying the slurry; pouring out the first slurry obtained in the step 2, drying in a 110 ℃ oven to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 6 hours at 1100 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:3 for wet ball milling, wherein the ball milling time is 5 hours, and the rotating speed is 300rad/s, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring out the second slurry obtained in the step 5, drying in a baking oven at 100 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; burying the green body obtained in the step 6 at 1200 ℃ for sintering for 6 hours, wherein the specific heating operation is as follows: firstly, heating to 450 ℃ at a heating rate of 2 ℃/min, maintaining at the temperature for 2 hours, removing excessive PVA, and then continuously heating the sintering temperature at a heating rate of 1 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 3:
the embodiment provides a microwave dielectric ceramic material, the chemical formula of which is Mg 0.94 Cu 0.06 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 . X-ray diffraction (XRD) patterns are shown as d in fig. 1, and SEM patterns are shown as d in fig. 2; as can be seen from the figure, the crystal grain morphology is a polyhedron coexisting with a rod-like shape.
A preparation method of a ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.94 Cu 0.06 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:3 for wet ball milling, wherein the ball milling time is 6 hours, and the rotating speed is 220rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring out the first slurry obtained in the step 2, drying in a 110 ℃ oven to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 5 hours at the temperature of 1000 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:3 for wet ball milling, wherein the ball milling time is 5 hours, and the rotating speed is 220rad/min, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring out the second slurry obtained in the step 5, drying in a baking oven at 100 ℃, adding a polyvinyl alcohol (PVA) solution with the concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; sintering the green body obtained in the step 6 for 4 hours at 1150 ℃, wherein the specific heating operation is as follows: firstly, heating to 600 ℃ at a heating rate of 5 ℃/min, maintaining the temperature for 2 hours, removing redundant PVA,then continuously heating the sintering temperature at a heating rate of 3 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 4:
the embodiment provides a microwave dielectric ceramic material, the chemical formula of which is Mg 0.92 Cu 0.08 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 . X-ray diffraction (XRD) patterns are shown as e in fig. 1, and SEM patterns are shown as e in fig. 2; as can be seen from the figure, the crystal grain morphology is a rod-like structure.
The preparation method of the ultra-low loss niobic acid system microwave dielectric ceramic material is characterized by comprising the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.92 Cu 0.08 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:2 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 240rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in a drying oven at 90 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 4 hours at 1050 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:2 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 240rad/min, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in a baking oven at 90 ℃, adding a polyvinyl alcohol (PVA) solution with the concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the green body obtained in the step 6 is buried in powder material (namely a matrix) with the same components of the green body, and is sintered for 5 hours at 1150 ℃, and the specific heating operation is as follows: firstly, heating to 500 ℃ at a heating rate of 4 ℃/min, maintaining at the temperature for 1 hour, removing excessive PVA, and then continuously heating the sintering temperature at a heating rate of 2 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 5:
the embodiment provides a microwave dielectric ceramic material, the chemical formula of which is Mg 0.9 Cu 0.1 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 . X-ray diffraction (XRD) patterns are shown as f in fig. 1, and SEM patterns are shown as f in fig. 2; as can be seen from the figure, the crystal grain morphology is a rod-like structure.
A preparation method of an ultralow-loss niobic acid system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.9 Cu 0.1 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: the method comprises the steps of taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:5:2 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 260rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in a drying oven at 90 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 3 hours at 1050 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: the zirconia balls are used as ball milling media, deionized water is used as solvent, raw materials, the zirconia balls and the deionized water are placed in a planetary ball mill according to the mass ratio of 1:5:2 for wet ball milling, the ball milling time is 3 hours, and the rotating speed is 260rad/min, so that second slurry is obtained;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in a baking oven at 90 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the green body obtained in the step 6 is buried in powder material (namely a matrix) with the same components of the green body, and is sintered for 3 hours at 1150 ℃, and the specific heating operation is as follows: firstly, heating to 500 ℃ at a heating rate of 3 ℃/min, maintaining at the temperature for 2 hours, removing excessive PVA, and then continuously heating the sintering temperature at the heating rate of 2 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 6:
the embodiment provides a microwave dielectric ceramic material with a chemical formula of Mg 0.96 Cu 0.04 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 。
A preparation method of an ultralow-loss niobic acid system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 According to the chemical general formula Mg 0.96 Cu 0.04 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:5:3 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 280rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in a drying oven at 90 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 2 hours at 1050 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:5:3 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 280rad/min, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in a baking oven at 90 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the green body obtained in the step 6 is buried in powder material (namely a matrix) with the same components of the green body, and is sintered for 6 hours at 1150 ℃, and the specific heating operation is as follows: firstly, raising the temperature to 400 ℃ at a heating rate of 2 ℃/min, maintaining the temperature for 3 hours, removing excessive PVA, and then continuing to raise the temperature at the heating rate of 3 ℃/minRaising the sintering temperature to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 7:
the embodiment provides a microwave dielectric ceramic material with a chemical formula of Mg 0.96 Cu 0.04 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 。
A preparation method of an ultralow-loss niobic acid system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 According to the chemical general formula Mg 0.96 Cu 0.04 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: the method comprises the steps of taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:2.5 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 300rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in a drying oven at 90 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 3 hours at 1050 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: the zirconia balls are used as ball milling media, deionized water is used as solvent, raw materials, the zirconia balls and the deionized water are placed in a planetary ball mill according to the mass ratio of 1:4:2.5 for wet ball milling, the ball milling time is 3 hours, and the rotating speed is 300rad/min, so that second slurry is obtained;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in a baking oven at 90 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the green body obtained in the step 6 is buried in powder material (namely a matrix) with the same components of the green body, and is sintered for 5 hours at the temperature of 1250 ℃, and the specific heating operation is as follows: firstly, heating to 500 ℃ at a heating rate of 2 ℃/min, maintaining at the temperature for 2 hours, removing excessive PVA, and then continuously heating the sintering temperature at the heating rate of 2 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Example 8:
the embodiment provides a microwave dielectric ceramic material with a chemical formula of Mg 0.94 Cu 0.06 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 。
A preparation method of an ultralow-loss niobic acid system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 According to the chemical general formula Mg 0.94 Cu 0.06 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: the method comprises the steps of taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:2.5 for wet ball milling, wherein the ball milling time is 3 hours, and the rotating speed is 210rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring the first slurry obtained in the step 2, drying in a drying oven at 90 ℃ to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 4 hours at 1050 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: the zirconia balls are used as ball milling media, deionized water is used as solvent, raw materials, the zirconia balls and the deionized water are placed in a planetary ball mill according to the mass ratio of 1:6:2.5 for wet ball milling, the ball milling time is 3 hours, and the rotating speed is 210rad/min, so that second slurry is obtained;
step 6: granulating and pressing a green body; pouring the second slurry obtained in the step 5, drying in a baking oven at 90 ℃, adding a polyvinyl alcohol (PVA) aqueous solution with the mass concentration of 12% into the baking oven after crushing treatment, granulating through a 80-120-mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the green body obtained in the step 6 is buried in powder material (namely a matrix) with the same components of the green body, and is sintered for 4 hours at the temperature of 1100 ℃, and the specific heating operation is as follows: firstly, heating to 450 ℃ at a heating rate of 1 ℃/min, maintaining at the temperature for 2.5 hours, removing excessive PVA, and then continuously heating the sintering temperature at the heating rate of 2 ℃/min to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
Fig. 1 is an X-ray diffraction (XRD) pattern of samples of different Cu substitution amounts (x= 0,0.02,0.04,0.06,0.08,0.1) provided in an embodiment of the present invention. As can be seen from FIG. 1, the ceramic materials obtained by different Cu substitution amounts are all pure phase MgZrNb 2 O 8 This indicates that Cu ions enter MgZrNb 2 O 8 The crystal lattice does not form a second phase and does not change MgZrNb 2 O 8 Is a ceramic crystal phase structure.
Fig. 2 is an SEM image of samples with different Cu contents (x= 0,0.02,0.04,0.06,0.08,0.1) according to various embodiments of the present invention. It can be seen that the grains of the sample without Cu substitution did not grow sufficiently and some small grains and voids were observed. When x is more than or equal to 0.02 and less than or equal to 0.04, the grains start to grow up, and the average grainsIncreased size, indicating Cu 2+ Ion substitution promotes grain growth. As Cu content continues to increase, rod-like grains appear, probably due to grain growth and grain boundary diffusion. It can be concluded that Cu substitution can promote grain growth, achieving a high degree of densification of the ceramic.
Table 1 shows the dielectric properties of samples of different Cu contents (x= 0,0.02,0.04,0.06,0.08,0.1) provided by different examples. Since Cu ions have a higher polarizability than Mg ions, the dielectric constant thereof tends to be gradually increased. Meanwhile, cu ions are substituted to promote grain growth, so that the grain size is increased (namely grain boundaries are reduced), and holes are reduced. The presence of grain boundaries is often a two-dimensional defect and can disrupt the long-range order of the crystal, resulting in dielectric loss. Grain boundaries are closely related to grain size, and the total number of grain boundaries decreases as the average grain size increases. Thus Cu ion substitution reduces dielectric losses.
TABLE 1
Figure BDA0002952571760000111
Figure BDA0002952571760000121
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.

Claims (2)

1. A kind of ultralow loss zirconium magnesium niobate system microwave dielectric ceramic material, characterized by that:
the chemical formula is Mg 0.96 Cu 0.04 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 The crystal grain form is that polyhedron and rod-like shape coexist;
the preparation method of the ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.96 Cu 0.04 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:3 for wet ball milling, wherein the ball milling time is 6 hours, and the rotating speed is 300rad/s, so as to obtain first slurry;
step 3: drying the slurry; pouring out the first slurry obtained in the step 2, drying in a 110 ℃ oven to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 6 hours at 1100 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:6:3 for wet ball milling, wherein the ball milling time is 5 hours, and the rotating speed is 300rad/s, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring out the second slurry obtained in the step 5, drying in a 100 ℃ oven, crushing, adding a polyvinyl alcohol PVA aqueous solution with the mass concentration of 12%, sieving with a 80-120 mesh sieve, granulating, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; the raw material obtained in the step 6 is processedSintering the blank at 1200 ℃ for 6 hours, wherein the specific heating operation is as follows: firstly, heating to 450 ℃ at a heating rate of 2 ℃ per minute, maintaining the temperature for 2 hours, and then continuously heating the sintering temperature at a heating rate of 1 ℃ per minute to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
2. A kind of ultralow loss zirconium magnesium niobate system microwave dielectric ceramic material, characterized by that: the chemical formula is Mg 0.94 Cu 0.06 ZrNb 2 O 8 The crystal phase is pure phase MgZrNb 2 O 8 The crystal grain form is that polyhedron and rod-like shape coexist;
the preparation method of the ultralow-loss zirconium magnesium niobate system microwave dielectric ceramic material comprises the following steps:
step 1: batching; raw material MgO, cuO, zrO 2 And Nb (Nb) 2 O 5 Respectively according to chemical formula Mg 0.94 Cu 0.06 ZrNb 2 O 8 The stoichiometric ratio of the raw materials is used for proportioning, and the purities of the raw materials are all more than 99 percent;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:3 for wet ball milling, wherein the ball milling time is 6 hours, and the rotating speed is 220rad/min, so as to obtain first slurry;
step 3: drying the slurry; pouring out the first slurry obtained in the step 2, drying in a 110 ℃ oven to obtain a dried mixture, and then crushing the dried mixture through a 120-mesh standard sieve to obtain dry powder;
step 4: presintering; placing the dried powder obtained in the step 3 into an alumina crucible, presintering for 5 hours at the temperature of 1000 ℃ to enable the uniformly mixed powder to perform a pre-reaction to obtain presintering powder;
step 5: ball milling; ball milling is carried out on the presintered powder obtained in the step 4, and the specific ball milling process is as follows: taking zirconium dioxide balls as ball milling media, taking deionized water as solvent, placing raw materials, zirconium balls and deionized water into a planetary ball mill according to the mass ratio of 1:4:3 for wet ball milling, wherein the ball milling time is 5 hours, and the rotating speed is 220rad/min, so as to obtain second slurry;
step 6: granulating and pressing a green body; pouring out the second slurry obtained in the step 5, drying in a 100 ℃ oven, adding a polyvinyl alcohol (PVA) solution with the concentration of 12% into the oven after crushing treatment, granulating by a 80-120 mesh sieve, and pressing under 8-10 Mpa to form a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7: sintering; sintering the green body obtained in the step 6 for 4 hours at the temperature of 1150 ℃, wherein the specific heating operation is as follows: firstly, heating to 600 ℃ at a heating rate of 5 ℃ per minute, maintaining the temperature for 2 hours, and then continuously heating the sintering temperature at a heating rate of 3 ℃ per minute to obtain the pure phase MgZrNb 2 O 8 Is a ceramic material of the ceramic material.
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